Abstract: Nano-SiO₂ doping has become an effective way to improve the performance of methyl vinyl silicone rubber (MVSR). However, nano-SiO₂ is easy to agglomerate. When it is directly mixed into MVSR matrix, nano-SiO₂ is difficult to disperse in MVSR matrix, resulting in poor adhesion effect of SiO₂-MVSR molecular interface, defects in the molecular interface and other adverse effects, so that the purpose of improving MVSR performance cannot be achieved. In order to improve the adhesion of SiO₂-MVSR molecular interface and make nano-SiO₂ more easily dispersed in MVSR matrix, this paper constructed the SiO₂-MVSR molecular interface models that unmodified and modified by KH550, KH560, KH570 and KH792, and carried out structural optimization and molecular dynamics calculation. By comparing the adhesion energies, adhesion depths and adhesion thermal stabilities of the molecular interface in different models, the reason for the improvement of the adhesion of SiO₂-MVSR molecular interface modified by silane coupling agents was analyzed from the perspective of molecular structure. The results show that the key to improve the adhesion of SiO₂-MVSR molecular interface is to select the non-hydrolytic group of the silane coupling agents. When the proportion of the same chemical bond between the non-hydrolytic group and MVSR molecular chain is larger, and the number of more electronegative atoms is more, the effect of improving the adhesion of SiO₂-MVSR molecular interface is better. At the same time, the longer chain length and larger relative molecular weight of silane coupling agent will also help to improve the adhesion.